Rubberlike product



Patent ed July 16, 1940 UNITED STATES PATENT OFFICE nuansnmm rnonuc'r Harvey G. Kittredge, Dayton, Ohio, assignor to The Kay & Ess Chemical Corporation, Dayton, Ohio, a corporation of Delaware No Drawing. Application January 6, 1937,

Serial No. 119,311

4C'laims.

It is my object to utilize a heretofore useless a by-product as one of the elements in the manum facture of my new product.

It is my object to utilize the polymers produced by the long heating of vegetable oils, such as tung oil, oiticica oil, perilla oil, linseed, soya. cottonseed and the like, either with or without a 15 catalyst to hasten polymerization.v These poly-. mers have been long considered of no value, and in the use of these oils, particularly tung, oiticica and perilla in connection with the making of varnishes, it has been customary to take steps to prevent the polymers of such oils "occurring, as

' the gelatinous nature of these polymers are useless for any useful purpose.

. It is my object to provide a reaction product of a polymer of a vegetable oil and a polyhl'dric 33 alcohol and to secure a liquid or plastic that is easily thereafter vulcanized as natural rubber is vulcanized. My product being liquid or plastic, is easily incorporated in rubber or with reinforcing materials, or as a coating for textiles,

3o metals and the like, upon which it can be baked.

Heretofore, rubber substitutes have been diilicult of application because of their plastic or solid nature requiring expensive milling and other handling in connection with their manua facture or with their mixture with natural rubber.

. The particular object of my invention is to carry the oil change to a solid or semirsolid, de-

pending on the type of the oil. In other words,

it is my object to carry the polymerization to substantially the ultimate stage, which, in the case of China-wood oil or tung oil, is a relatively stifi, gelatinous polymer, while the polymers oi.

oiticica and perilla are somewhat softer. 4p Heretofore this substantially complete polymer,

it accidentally secured, was thought useless and every eflort was made to avoid it. It is the obiect of my invention to use it for the purposes hereinafter described.

Pmuuc'rrou or ran REACTION Pnoouc'r I have utilized the polymers of tuna oil, oiticica Example 1 For instance, I have combined 100 grams of the polymer or tung oil'and 35 grams of glycerol. This mixture was heated at a temperature between 410 degrees and 450 degrees Fahrenheit. The'heating was continued until all of the glycerol and tung' oil polymers were. combined. The resulting product is a reddish material that is viscous in its physicalcharacter.

Example 2 One hundred eleven grams of phthalic anhydride and 46 grams of glycerol were heated onehalf hourat 410 degrees Fahrenheit. To this 1' product was then added 290 grams of the combination of oiticica oil polymer or other vegetable oil polymer and glycerol. The heating was continued'at 410 degrees Fahrenheit until clear, held at this temperature for an additional hour,. then the temperature'was raised to 500 degrees Fahrenheit, and then the mass was allowed to cool. The resulting product is resilient and elastic.

The resiliency and elasticity can be varied between wide limits, depending upon the amount of the vegetable 'oil-polymer-glyceride that is added? By the addition of a small percentage of sulphur of approximately 3 per cent, the rubberlikecharacter of the mass is appreciably increased. It may be stretched, and upon release, 0 shrink substantially to its original size. Tung oil and perilla oil polymers may be substituted for the oiticica oil polymers in this example.

Vuncnmzarron rubber, which is elastic and resilient, which may be compressed and returned to its original shape,

- has good cohesion, and which is resistant to superficial oxidation andis inert to many of the acids and alkalis, oils and greases that affect ad- 5 versely natural rubber.

The exact character of the resulting product depends upon the vulcanizing agents, accelerators and deoxidants employed, as well as upon the nature of the fillers, such as zinc oxide, car bon black, zinc sulphide and other pigments.

For instance:

Example 3 One hundredgrams of'the reaction product of the polymers or vegetable oil and glycerol mixed 5 V 2 with three or more grams of sulphur and heated for several minutes results in the rubberlike compound described herein.

One of the advantages of this product is the absence of free sulphur after vulcanization. It can be employed in mixing with natural rubber without any disadvantage of having free sulphur in the mixture, which is the present disadvantage of many substitute rubber-like compounds now being used in the art.

I have found that this reaction product of, vegetable oil polymers with glycerol is an efiective plasticizer for cellulose acetate and nitrate lacquers.

Example 4 A stifl elastic and resilient product is produced as follows:

Thirty-five grams .of a combined polymer of a vegetable oil such as either China-wood oil, oiticica oil, perilla oil and glycerol and 6 to 12 grams maleic acid or phthalic acid or anhydride, or succinic acid.

The foregoing is heated at 365 degrees F. until the mass begins to get relatively heavy, then at 280 degrees F. for two hours. Theresulting product is a dark brown resilient and elastic mass that can be stretched and returned to its original size and shape. It is inert to oils, greases and to such acids as hydrochloric, dilute nitric and such alkalis as caustic soda and potash.

When it is desired to mix the reaction products described herein directly with rubber or with a synthetic rubberlike compositionsuch as polymerized chloroprene, oleflne polysulfide or with one of the glycerol phthalate resins, this can be done by using from 10 to 90 per cent of the or synthetic rubber.

reaction productof this invention with rubber plasticnature of my reaction products, it is possible to mill such a product with the rubber or synthetic rubber without dimculty. It gives to the product resulting that tack and adhesion which I have found desirable in this connection. After the mixture, the rubber or synthetic rub- By reason of the liquid or I ber can be vulcanized in the usual manner.

Any one of the following accelerators may be used when the vulcanization oi the product covered by this application is carried out, such as zinc dimethyldithiocarbamate, lead dimethyldithiocarbamate, mercaptobenzothiazole and benzothiazyl di'sulfide.

The vulcanizing agents referred to herein may be any one of several, such as sulphur.

This application is a continuation in part of my application, Ser. No. 78,486, filed May 7, 1936, Patent No. 2,111,427.

It will be understood that I desire to comprehend within my invention such modifications as may be necessary to adapt it to varying conditions and uses.

Having thus fully described my invention, what I claim as new and desire to secure by Letters Patent is:

1. A rubberlike product comprising a vulcanized mixture of oleflne polysulflde and a reaction.

product of glycerol phthalate with a polymer of vegetable oil which has been substantially com- 'tinous state and combined with glycerol.

3. A rubberlike product obtained by reacting 

